CN101018828A - Electroconductive resin composition, production method and use thereof - Google Patents

Electroconductive resin composition, production method and use thereof Download PDF

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CN101018828A
CN101018828A CNA2005800308774A CN200580030877A CN101018828A CN 101018828 A CN101018828 A CN 101018828A CN A2005800308774 A CNA2005800308774 A CN A2005800308774A CN 200580030877 A CN200580030877 A CN 200580030877A CN 101018828 A CN101018828 A CN 101018828A
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carbon fiber
resin composition
quality
resin
conductive resin
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长尾勇志
山本龙之
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Resonac Holdings Corp
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Showa Denko KK
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Abstract

The electroconductive resin composition comprising 1 to 30 mass % of carbon fiber having a hollow structure, an average filament diameter of 50 to 500 nm and an average aspect ratio of 50 to 1000 and 99 to 70 mass % of resin, wherein the volume ratio of carbon fiber agglomerate to one carbon fiber filament constituting the agglomerate in the resin composition(volume of carbon fiber agglomerate/volume of a carbon fiber filament) is 1500 or less according to the invention can be uniformly dispersed in resin without agglomeration and therefore, a good electroconductivity can be achieved by addition of small amount of the composition.

Description

Conductive resin composition and production method thereof and purposes
The cross reference of related application
The application that this paper submits to according to 35 U.S.C.Section 111 (a), require to submit on September 21st, 2004 according to 35 U.S.C.Section119 (e) (1) according to 35 U.S.C.111 (b) clause, sequence number is the right of 60/611,267 U.S. provisional application.
Technical field
The present invention relates to a kind of conductive resin composition, it can be evenly dispersed in the agglomerate that does not form conductive filler material in the matrix of resin such as thermoplastic resin, thermosetting resin or light-cured resin in matrix.
More specifically, the present invention relates to a kind of conductive resin composition and production method thereof, wherein has few branched carbon fiber (starting material are formed and starting material concentration prepares by regulating) in reaction process by use, the agglomeration of carbon fiber can easily be removed and can not break filament with mixed with resin the time, and can form three-dimensional net structure in the resin combination that contains the small amount of carbon fiber of gained.
In addition, the present invention relates to a kind of conductive resin composition, the filler material that it does not make physical strength descend as giving electroconductibility, or as the electronic emission material of FED (field-emitter display), when the time as the material of transparency electrode, electromagnetic shielding, static inhibitor, electrically conducting coating, electroconductive binder or secondary cell.
Background technology
Carbon fiber is used in the various matrix materials owing to its good character such as high strength, snappiness and high conductivity.Along with recent development of electronic technology, expect carbon fiber as the filler in the antistatic coating of the conductive filler material that uses in electromagnetic shielding material, the static inhibitor, resin or the filler of transparent conductive resin.And because the height of carbon fiber slidably property (slidability) and wear resistance, expectation is used for brush and adjustable resistor with it.In addition, has the carbon fiber of high conductivity, thermal conductivity and electromigration resisting property as the attention that is attracting people such as the wiring material in the device of LSI.
The filament diameter of polyacrylonitrile carbon fiber (PAN), asphalt-based carbon fiber, Mierocrystalline cellulose carbon fiber etc. is big relatively, be 5～10 μ m, the conventional organic fibre of carbonization prepares these fibers by thermal treatment under inert atmosphere, and the electroconductibility of these fibers is so not good.Therefore, these carbon fibers have been widely used as the supporting material of resin, pottery etc.
Use is mainly only comprised as the reason of reinforced filling material by organic fibre deutero-carbon fiber: fiber is an inflexibility, consequently broken filaments when fiber and resin kneading; The electroconductibility that obtains expectation need add about 30 quality %; The thickness of filament and rigidity cause fiber filaments in the shaping prod towards same direction in addition.As a result, following point is arranged, the anisotropy of contraction causes the distortion of shaping prod, and appears at the roughness that surperficial carbon fiber filament causes that shaping prod is surperficial suitable.
Owing to above reason, think that comprising resin combination by organic fibre deutero-carbon fiber is not suitable for precision modulding (wherein the resin of high-insulation is endowed electroconductibility with dissipating static electricity, and need dimensional precision), and be not suitable for molded (wherein need the surface of good slickness, do not have) of electronic package owing to contact the scratch that produces with housing.
In the eighties in 20th century, begun research to vapor-grown carbon fibers, therefore thermolysis in the presence of transition-metal catalyst produces this carbon fiber by gas such as hydrocarbon, can obtain to have the carbon fiber of the filament of the about 0.1～about 0.2 μ m of diameter (about 100～about 200nm).
Recently, carry out the research to carbon nanotube just energetically, described carbon nanotube has the filament diameter littler than vapor-grown carbon fibers.The example of the production method of carbon nanotube comprises arc discharge method, laser ablation and chemical vapour sedimentation method.For example, in the arc discharge method,, produce 3000 ℃ or higher high temperature thus, make the evaporation of carbon and catalyzer and in process of cooling, produce carbon nanotube by the catalyst metal surface by carrying out arc discharge between the electrode that is combined in catalyst metal wherein having.
Usually, most of filament of the vapor-grown carbon fibers of generation or carbon nanotube is collected as the settling of laminar form or agglomerate form, and wherein filament tangles each other.The settling of collecting is difficult to be dispersed in the resin etc. (referring to United States Patent (USP) 6 like this, 608,133), therefore, after pulverize (1), settling uses ball mill, sand mill etc. to make it and mixed with resin, as pre-treatment (referring to JP-A-2003-308734), or (2) proposed a kind of method (JP-A-2002-347020) recently, wherein when settling and resin are mediated, make the settling fragmentation by rubbing (solid state shear), and be dispersed in the resin thus.
Above method (1) is characterised in that, makes sedimental big agglomerate broken and be reduced to fritter, makes thus that settling is easier to be dispersed in the resin.But, by using the kneading method of standard forcing machine, can not make the piece of agglomerate further be reduced to thinner piece, therefore, do not add a large amount of fillers, can not form conductive network.Conductive network herein is made of fine agglomerate.
In back one method (2), when mediating resin, apply high shear force, and when pulverizing agglomerate, pulverize filler, all even list of conductive filler material is disperseed.But, in order to give electroconductibility,, report that the length-to-diameter ratio of filler particles is big more in resin, adding under the situation of conductive filler material, it is more little to obtain the needed amount of filler of electroconductibility.In this method, wherein when pulverizing filler, carry out the pulverizing of agglomerate, the value or the advantage of vapor-grown carbon fibers or carbon nanotube reduce by half.Compare with ideal production method (vapor-grown carbon fibers or even carbon nanotube are dispersed in the resin and not fracture of filament), forming conductive network needs a large amount of fillers.
Summary of the invention
The present invention solves above traditional problem, and provide a kind of conductive resin composition, it prepares by each carbon fiber filament is evenly dispersed in the resin as far as possible, this resin has the conductive filler material than ordinary method less amount, thereby resin combination can obtain the same high or higher electroconductibility with conventional resin combination, form conductive network thus effectively, the production method of conductive resin composition also is provided.
In order to make resin combination obtain the same high or higher electroconductibility with conventional resin combination with the conductive filler material of less amount, importantly by controlling the raw-material composition and the concentration of filler, and further control the concentration of vapor-grown carbon fibers in the production process, prevent that the carbon fiber filament from tangling each other three-dimensionally.On the other hand, the inventor finds, with the mixing of resin in, importantly (1) suppresses shearing force in resin and conductive filler material blended process, reduce the fracture of filament thus as much as possible, (2) prevent in the kneading process conductive filler material diffusion exceedingly in matrix resin, form thus and keep showing the necessary network structure of electroconductibility.
The inventor has studied the character and the kneading method of filler, and find, by making filler not keep the agglomerate form in conductive resin composition, the resin combination that forms conductive network effectively can be endowed high electroconductibility under the situation that adds small amount of filler.In addition, the inventor confirms that the minimizing of carbon fiber mixed resultant and the homodisperse of carbon fiber prevent that resin inherent physical strength from reducing.
According to the present invention, provide following conductive resin composition and production method thereof.
1, a kind of conductive resin composition, it comprises the carbon fiber of 1～30 quality % and the resin of 99～70 quality %, this carbon fiber has hollow structure, average filament diameter is 50～500nm, average aspect ratio is 50～1000, and wherein the volume ratio (volume of the volume of carbon fiber agglomerate/carbon fiber filament) of a carbon fiber filament of carbon fiber agglomerate and formation agglomerate is 1500 or littler in the resin combination.
2, according to 1 conductive resin composition, wherein the BET specific surface area of carbon fiber is 3～50m 2/ g, mean level of the sea spacing d 0002Be 0.345nm or littler, and in raman scattering spectrum, 1341～1349cm -1Bands of a spectrum (Id) and 1570～1578cm -1The ratio of peak (Id/Ig) of bands of a spectrum (Id) be 0.1～1.4.
3, according to 1 conductive resin composition, wherein every of carbon fiber filament have 5 or still less from the branched part of filament surfaces.
4, according to 1 conductive resin composition, wherein resin is thermoplastic resin, thermosetting resin or light-cured resin.
5, according to 1 conductive resin composition, wherein the mean diameter of carbon fiber agglomerate is 0.2～10 μ m in the resin combination.
6, according to 1 conductive resin composition, wherein the area ratio of carbon fiber agglomerate in any cross section of resin combination is 5% or littler.
7, according to 1 conductive resin composition, wherein the volume resistance value is 10 10Ω cm or littler.
8, according to 7 conductive resin composition, wherein resin combination is 0.9 or bigger with the ratio (conductive resin composition/resinogen material) of the raw-material shock resistance value of resin.
9, a kind of method of producing conductive resin composition, wherein the carbon fiber with 1～30 quality % mixes with the molten thermoplastic resin of 99～70 quality %, and this carbon fiber has hollow structure, and average filament diameter is 50～500nm, average aspect ratio is 50～1000, and mixing energy is 1000MJ/m 3Or it is littler.
10, a kind of method of producing conductive resin composition, wherein with the liquid thermosetting mixed with resin of carbon fiber and 99～70 quality % of 1～30 quality %, this carbon fiber has hollow structure, and average filament diameter is 50～500nm, average aspect ratio is 50～1000, and mixing energy is 1000MJ/m 3Or it is littler.
11, a kind of method of producing conductive resin composition, wherein the carbon fiber with 1～30 quality % mixes with the liquid light-cured resin precursor of 99～70 quality %, this carbon fiber has hollow structure, average filament diameter is 50～500nm, average aspect ratio is 50～1000, and mixing energy is 1000MJ/m 3Or it is littler.
12, a kind of method of producing conductive resin composition, wherein supply the thermoplastic resin particle of 99～70 quality % from the hopper of kneader, and the carbon fiber of side loading 1～30 quality %, this carbon fiber has hollow structure, average filament diameter is 50～500nm, and average aspect ratio is 50～1000.
13, a kind of method of producing conductive resin composition, the thermoplastic resin powder who wherein supplies 99～70 quality % mixes with the carbon fiber of 1～30 quality %, this carbon fiber has hollow structure, average filament diameter is 50～500nm, average aspect ratio is 50～1000, then mixture is carried out melt kneading.
14, a kind of method of producing conductive resin composition, wherein the thermosetting resin with 99～70 quality % mixes with the carbon fiber of 1～30 quality %, and this carbon fiber has hollow structure, and average filament diameter is 50～500nm, average aspect ratio is 50～1000, then mixture is carried out thermofixation.
15, use the antistatic material of each described conductive resin composition in 1～8.
16, use the electrically conducting coating of each described conductive resin composition in 1～8.
17, use the electroconductive binder of each described conductive resin composition in 1～8.
According to the present invention,, the mechanical properties of matrix resin is descended owing to can show electroconductibility by adding the small amount of carbon fiber.Therefore, provide have the surface of good slickness, dimensional precision and glossy conductive resin composition.
The accompanying drawing summary
Fig. 1 represents the optical microscopy map (* 1000) of the cross-sectional view of the plate of preparation among the embodiment 1.
Fig. 2 represents the analytical results of agglomerate diameter in the microgram shown in Figure 1.
Preferred forms
The present invention is below described in more detail.Being used for the carbon fiber with hollow structure of the present invention can prepare by using the thermolysis of transistion metal compound organifying compound.
Raw-material organic compound about as carbon fiber can use aromatic hydrocarbon such as toluene, benzene or naphthalene, the mixture of gas such as ethene, acetylene, ethane, Sweet natural gas or carbon monoxide or these gases.In these materials, aromatic hydrocarbon such as toluene or benzene are preferred.
Organo-transition metal compound is the compound that comprises transition metal (as catalyzer).The example of transition metal comprises the metal that belongs to periodictable 4～10 families.In these compounds, the compound that comprises ferrocene or nickelocene is preferred.
About catalyst adjuvant, can use sulphur compound such as sulphur or thiophene, this catalyst adjuvant is removed for example hydrogen of the gas that is adsorbed in synthetic/reaction atmosphere on the transition-metal catalyst particle surface effectively, improves catalytic activity thus.
By using reducing gas such as hydrogen as carrier gas, be fed in the reactor that is heated to 800～1300 ℃ with above-mentioned organic compound, organo-transition metal compound with for the sulphur compound of optional components, and react each other, produce carbon fiber thus.
About raw-material form, for example can use to be dissolved in as organo-transition metal compound in the raw-material aromatic hydrocarbon and sulphur compound, perhaps can use the material that under 500 ℃ or lower temperature, gasifies.But, at starting material is under the situation of liquid form, occurs raw-material evaporation and decomposition on the inwall of Reaktionsofen (reaction tubes), and this causes uneven concentration distribution, wherein starting material concentration is partly at some part height, thereby the often agglomeration of carbon fiber that produces.Therefore, about raw-material form, evenly inner at reaction tubes in order to make concentration of material, Qi Hua starting material are preferred in advance.
Transition-metal catalyst is preferably 15～35 quality % with the ratio (transition metal/transition metal+sulphur compound (atomic ratio)) of sulphur compound catalyst adjuvant.If this ratio is less than 15 quality %, it is too high that catalyst activity becomes, and can increase in the carbon fiber branched quantity or produce radially carbon fiber, and this causes forming strong agglomerate inadvisablely.If this ratio surpasses 35 quality %, owing to can not remove gas such as the hydrogen (this upset is fed to the carbon source of catalyzer, and causes reaction product to become particle) that is adsorbed onto on the catalyzer fully, so inadvisable.
Starting material concentration when the branch quantity of carbon fiber and the releasing degree of filament agglomerate depend on reaction.That is to say, when the material concentration in the vapor phase is high, form granules of catalyst by the heterogeneous nucleogenesis on the carbon fiber surface that generates, and generate other carbon fiber, form carbon fiber thus as silver frost (silver frost) from carbon fiber surface.And the carbon fiber filament that is obtained by the material with high density tangles easily each other, and can not easily untie.Therefore, the preferred 1g/l of ratio of the load volume (l) in raw-material supply (g) and the reaction tubes or littler, 0.5g/l more preferably, even 0.2g/l more preferably.
In order to improve the binding property with resin, preferably in inert atmosphere, remove organic substance such as the tar that sticks on the carbon fiber surface by thermal treatment under 900～1300 ℃.And, in order to improve the electroconductibility of carbon fiber, preferably in inert atmosphere, heat-treat under 2000～3500 ℃, thus growing crystal.
This stove is used for thermal treatment and can be any stove, as long as can keep 2000 ℃ or higher target temperature, more preferably 2300 ℃ or higher with the stove of growing crystal.For example, can use acheson furnace, resistance furnace or high frequency furnace.Selectively, in some cases can be by heat-treating on the product that directly applies electrical current to powdered material or formation.
Heat treated atmosphere is non-oxide, is preferably by one or more inert atmospheres formed in argon, helium and the neon.About heat treatment time, according to productivity, the time is short more preferred more, and common 1 hour is enough.
For the crystallization of further growth carbon fiber and improve electroconductibility thus, in the process that can in inert atmosphere, heat-treat under 2000～3500 ℃, with boron compound such as norbide (B 4C), boron oxide (B 2O 3), element boron, boric acid (H 3BO 3) or borate be mixed in the carbon fiber.
The add-on of boron compound depends on the chemical property and the physical properties of compound, and is not particularly limited.For example, using norbide (B 4C) under the situation, add-on is preferably 0.5～10 quality % of carbon fiber, more preferably 0.1～5 quality %.
By adding the thermal treatment of boron compound, improved the carbon degree of crystallinity of carbon fiber and improved electroconductibility.In the carbon fiber crystal or the boron amount that comprises in the plane of crystal be preferably 0.01～5 quality %.For the avidity of the electroconductibility of improving carbon fiber and it and resin, more preferably boron content is 0.1 quality % or more.In addition, owing to be limited to about 3 quality % (boron can replace the carbon in the graphite flake (graphenesheet)) on the boron amount, a large amount of boron, especially 5 quality % or more boron are worthless, boron can keep as boron-carbide or boron oxide compound, thereby causes that electroconductibility descends.
In order to improve the avidity between carbon fiber and the resin, can make carbon fiber carry out oxide treatment, thus phenolic hydroxyl group, carboxylic group, quinonyl group or lactone groups are incorporated on the surface of carbon fiber.
In addition, can make carbon fiber use the surface treatment of silane coupling agent, titanate coupling agent, aluminum coupling agent or phosphate coupling agent etc.
But the vapor-grown carbon fibers branch is not as long as carbon fiber forms strong agglomerate.The branch amount of a filament preferred 5 or still less, more preferably 3 or still less.
The filament external diameter of used vapor-grown carbon fibers is 50～500nm among the present invention, preferred 90～250nm, more preferably 100～200nm.If the filament external diameter is less than 50nm, surface energy is exponentially to be increased, and significantly improves the ability of aggregation of filament thus.Under the situation of simple kneading agglomeration vapor-grown carbon fibers and resin, can not obtain sufficient dispersion.Because agglomerate is dispersed in the resinous substrates, can not form conductive network.If apply big shearing force in order to obtain to disperse fully in kneading process, thereby agglomerate can be interrupted in matrix and spread.But, when agglomerate is interrupted, also interrupted filament, can not obtain desired electroconductibility thus.
The length-to-diameter ratio of vapor-grown carbon fibers is 50～1000, and is preferred 55～800, more preferably 60～500.If length-to-diameter ratio is bigger, in other words, if thread-length is longer, filament can tangle each other, and can not easily untie, and therefore can not obtain sufficient dispersion.On the other hand, if length-to-diameter ratio less than 50, in order to be formed for obtaining the connection skeleton structure of electroconductibility, needs to increase combined amount, this causes the flowability of resin combination and tensile strength to descend, and is worthless.
The BET specific surface area of vapor-grown carbon fibers is preferably 3～50m 2/ g, more preferably 8～30m 2/ g, even more preferably 11～25m 2/ g.The BET specific surface area is big more, and surface energy is just big more, and this not only makes difficulties in dispersion, and causes with the resin-coating carbon fiber insufficient.As a result, in the time will preparing matrix material, big BET specific surface area is worthless, and this can cause electroconductibility and physical strength to descend.
Interplanar spacing d in the X-ray diffraction method 002Preferred 0.345nm or littler, more preferably 0.343nm or littler, even more preferably 0.340nm or littler.
In raman scattering spectrum, 1341～1349cm -1Bands of a spectrum (Id) and 1570～1578cm -1The ratio of peak (Id/Ig) of bands of a spectrum (Id) be preferably 0.1～1.4, more preferably 0.15～1.3, even more preferably 0.2～1.2.
In order to obtain electroconductibility, the vapor-grown carbon fibers planar degree of crystallinity on direction and the stacked direction is high more, preferred more.But, when the filament external diameter too hour because crooked influence, interplanar spacing is sometimes not little.That is to say, give resin electroconductibility needed connection skeleton structure in order to form, the dispersibility and the balance between the degree of crystallinity of vapor-grown carbon fibers are important, therefore, limit the interplanar spacing d in filament external diameter, length-to-diameter ratio, BET specific surface area, the X-ray diffraction method 002Scope with ratio of peak (Id/Ig) in the raman scattering spectrum.
Though resin used among the present invention is not particularly limited, resin will be selected from thermosetting resin, light-cured resin or thermoplastic resin.Wherein a kind of can the use separately, or they two or more can be used in combination.
The example of thermosetting resin comprises urea resin, melamine resin, xylene resin, phenol resins, unsaturated polyester, Resins, epoxy, furane resin, polyhutadiene, urethane, trimeric cyanamide phenol resins, silicone resin, polyamidoimide and silicone resin.
The example of thermoplastic resin comprises polyethylene, the ethylene-vinyl acetate copolymer resin, polypropylene, polystyrene, the AS resin, ABS resin, methacrylic resin, polyvinyl chloride, polymeric amide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, acetyl cellulose, Phthalic acid, diallyl ester, polyvinyl butyral acetal, polyvinyl alcohol, the vinyl acetate resin, ionomer, penton, ethene-alpha-olefin copolymer, ethylene-vinyl acetate copolymer, chlorinatedpolyethylene, vinyl chloride-vinyl acetate copolymer, 1, the 1-Ethylene Dichloride, vinylformic acid-vinyl chloride copolymer resin, AAS resin, the ACS resin, polyacetal, polymethylene amylene (polymethylene pentene), polyphenylene oxide, MODIFIED PP O, polyphenylene sulfide, butadiene styrene resin, thermoplastic polyurethane, poly-amino dimaleimide, polysulfones, polybutene, silicone resin, the MBS resin, methacrylic ester-styrene copolymer resin, polyamidoimide, polyimide, polyetherimide, polyacrylic ester, polyene propyl group sulfone, polyhutadiene, polycarbonate-methacrylic ester compound resin, polyethersulfone, polyether-ether-ketone, polyphtalamide, polymethylpentene (polymethyl pentene), tetrafluoroethylene resin, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/perfluoro alkyl vinyl ether (tetrafluoroethylene/perfluoroalkylvynilether copolymer) multipolymer, the tetrafluoroethylene/ethylene multipolymer, poly-vinylidene fluoride, polychlorotrifluoroethylene, chlorotrifluoroethylene/ethylene copolymer, polyvinyl chloride and liquid crystalline polymers.
About preparing the method for conductive resin composition of the present invention, for example when thermoplastic resin is used as resin, can use the method for wherein mediating every kind of component with conventional forcing machine or kneader.In order to prevent the fracture of fiber filaments, expectation is fed to carbon fiber the resin of molten state.In this case, screw rod speed of rotation and compound viscosity low more (low shearing speed and high temperature), the electroconductibility of acquisition is high more.Under the situation of using resin particle, than using hopper more to expect to supply carbon fiber by side loading.Using under the situation of toner, can in advance resin mixed with carbon fiber by using Henschel mixing machine etc., and feed in raw material with hopper.
Using under any situation of thermosetting resin and light-cured resin, though thermosetting resin and light-cured resin only can be solid (and being liquefied with reactive diluent, solvent etc. or by heating in use) sometimes, but viscous liquid (monomer or partially polymerized) normally at room temperature, therefore, kneading is easy, and the kneading energy that needs is compared much lower with the situation of using thermoplastic resin, so these resin materials are preferred.But, under condition of cure, (wherein applying solidification value or higher heat energy, perhaps apply luminous energy) to light-cured resin to thermosetting resin, resin can polymerization and is crosslinked, thereby is solidified into shaping prod, film (coating), tackiness agent etc.
In kneading, for example, under the situation of using thermosetting resin, by in room temperature to the temperature of solidification value, use the device identical with the situation of thermoplastic resin, with low screw rod speed of rotation and low compound viscosity (solidification value or lower temperature) process resin, can easily obtain high conductivity.
In fact carbon fiber used among the present invention shows very high dispersibility, so hybrid element needs not be powerful.The screw rod speed of rotation depends on compound productivity, but within the bounds of possibility, the screw rod speed of rotation is low more, and the fracture of carbon fiber and excessive dispersion can reduce manyly more, to show high conductivity thus.
In the rotten scope of resin can not take place, the kneading temperature was preferably high.By high temperature, can reduce the viscosity of shearing force and resin, and can control the fracture of filament and the excessive dispersion of carbon fiber.Mediate energy and depend on type, molecular weight and the resin of resin and the blending ratio of carbon fiber.But energy is more little preferred more.The preferred 1000MJ/m of energy 3Or littler, more preferably 900MJ/m 3Or it is littler.
The example of method of moulding comprises press forming method, extrusion molding method, vacuum forming method, blow-moulding process and injection molding method.
The degree of agglomeration of carbon fiber in resin can recently define according to the volume of carbon fiber agglomerate with a carbon fiber filament forming agglomerate.In conductive resin composition of the present invention, volume ratio (volume of the volume of carbon fiber agglomerate/carbon fiber filament) 1500 or littler, preferred 1000 or littler, more preferably 500 or littler, even more preferably 100 or littler.
Under the particulate situation, usually primary particle diameter more little, the diameter of agglomerate is more little.But, if the diameter of primary particle size less than submicron, agglomeration ability and sticking power increase, and the diameter of agglomerate can not be less than particular value.When this represented with the relation between agglomerate volume and the primary particle volume, for particular value (submicron) or bigger primary particle diameter, the ratio of agglomerate volume/primary particle volume was a constant.On the other hand, for the primary particle diameter less than particular value (submicron), owing to the primary particle diameter diminishes and the agglomerate constancy of volume, so the ratio of agglomerate volume/primary particle volume increases.That is to say that for the primary particle diameter less than particular value (submicron), degree of agglomeration increases.
Also be like this in carbon fiber.For example, have identical length-to-diameter ratio when two kinds, but the carbon fiber with different filament diameters is when comparing each other, for identical degree of agglomeration, at the agglomerate volume and form aspect the volume ratio of a carbon fiber filament of agglomerate, both are identical.And for the filament diameter less than particular value, volume ratio is that degree of agglomeration increases.
Along with degree of agglomeration increases, owing to carbon fiber can not disperse equably, and can not form conductive network effectively, and owing to increase with the part of resin-coating such as the internal portion of agglomerate, the mechanical properties of composition reduces.
If the agglomerate volume surpasses 1500 with the volume ratio of a carbon fiber filament forming agglomerate, the mechanical properties of composition significantly reduces, and this is worthless.
The mean sizes of carbon fiber agglomerate is 0.2～10 μ m in the resin combination, is preferably 0.4～8 μ m, more preferably 0.8～5 μ m.
Owing to the amount of surface functional group in (greying) carbon fiber with high-crystallinity is few, little to the bounding force of resin.If agglomerate size is big, the interfacial area between resin and the carbon fiber is big, and this causes at the interface separation and cracking.If the mean sizes of agglomerate surpasses 10 μ m, physical strength reduces by half on the intensity basis of resin only, and this is worthless.
In any cross section of resin combination, the area ratio of carbon fiber agglomerate is 5% or littler, preferred 3% or littler, more preferably 1% or littler.
The area ratio of carbon fiber agglomerate, in other words, agglomerate exist ratio or share relevant with cracking with interfacial separation, the relation of the size of similar and agglomerate.For the blending ratio of carbon fiber among the present invention, if area is difficult to form conductive path than surpassing 5%, the result causes the unsatisfied electroconductibility and the physical strength of resin combination.
Therefore, physical strength is descended, must reduce the size and the share of agglomerate in resin combination of agglomerate.
Embodiment
Be described more specifically the present invention below with reference to representative embodiment.But embodiment shown below only is explanation, and the present invention never is limited to this.
The method of the form parameter of measuring carbon fiber is described below.Following calculating mean sizes: with * 30,000 ratio of enlargement is got SEM (scanning electronic microscope) image in 30 visuals field, measures the diameter of 300 filaments with image analyzer (LUZEX-AP is made by NIRECO Coporation).The average thread-length of following calculating: the ratio of enlargement with * 3000 continuously and panorama get SEM (scanning electronic microscope) image in 30 visuals field, with the length of 300 filaments of image analyzer measurement.Calculate length-to-diameter ratio with average thread-length divided by average filament diameter.The sum of observed branch part is several 300 divided by filament in the analysis with above-mentioned thread-length, calculates the branch part mark of each root filament, as the branch degree of carbon fiber.
The method of the various character of measuring carbon fiber is described below.
(NOVA1000, by Yuasa Ionics, Inc. makes) measures the BET specific surface area with the nitrogen adsorption method.
In the interior mark of Si, measure mean level of the sea spacing d with x-ray powder diffraction instrument (Geigerflex is made by Rigaku Corporation) 002Measure the ratio of peak (Id/Ig) in the raman scattering spectrum with Raman spectrometer (LabRam HR is made by JobinYvon), wherein Id is 1341～1349cm -1The peak height of bands of a spectrum, Ig is 1570～1578cm -1The peak height of bands of a spectrum.
The method of the agglomerate in the parsing tree oil/fat composition is described below.
The preparation of analytic sample: use opticmicroscope shaping prod to be cut into the thin slice that thickness is 0.8～1.0 μ m, prepare analytic sample with slicing machine.Like this from the shaping prod on thickness direction the interval with 20 μ m downcut thin slice.
The observation of sample: fill thin slice to be used as analytic sample with whiteruss.By get the bright field-of-view image of TEM (transmission electron microscope) with * 1000 ratio of enlargement, come observation sample.Use the image analyzer LUZEX-AP binarization picture of making by NIRECOCoporation, and measure the agglomerate diameter and the agglomerate total area corresponding to circumference.
Can use the average agglomerate volume of the hypothesis spheroid that calculates by agglomerate diameter corresponding to circle, with ratio, determine the volume ratio of the carbon fiber filament of carbon fiber agglomerate and single composition agglomerate by the average carbon fiber filament volume of the hypothesis cylindrical pillars of average filament diameter and length computation.
Area is than being the agglomerate total area and the observation in 10 visuals field and the ratio of the measurement total area.
With four probe methods (Loresta HP MCP-T410, by Mitsubishi ChemicalCorporation make) measure resin combination less than 10 8The volume resistance value of Ω cm measures 10 with insulation resistance detector (R8340 is by the high resistance meter of Advantest Corporation manufacturing) 8Ω cm or above volume resistance value.
Measure cantilever shock resistance (Izod impact resistance) by using cantilever beam impact tester (by Toyo Seiki Kogyo, Co., Ltd. manufacturing) according to JIS K-7110.The specimen in use piece be shaped as 64mm (length), 12.7mm (thickness) and 3.2mm (width).About notch size, tip radius is 0.25mm, and notch depth is 2.54mm.
The production of carbon fiber 1:
Benzene, ferrocene and sulphur (mass ratio: 96: 3: 1) is admixed together, prepare liquid starting material thus.Utilize hydrogen be used as carrier gas with 75 ° jet angle with liquid starting material be ejected into make by SiC, be heated to 1,250 ℃ Reaktionsofen (internal diameter: 120mm φ, highly: 2,000mm) in.Raw-material supply rate is 12g/min, and the flow velocity of hydrogen is 60L/min.
Will by the product (100g) that above method obtains pack into the crucible that graphite makes (internal diameter: 100mm φ, highly: 150mm), and 1000 ℃ of bakings 1 hour down in argon gas atmosphere.Then, in argon gas atmosphere, make products obtained therefrom carry out greying 1 hour under 2,800 ℃.
The production of carbon fiber 2:
Benzene, ferrocene and thiophene (mass ratio: 92: 7: 1) is admixed together, prepare liquid starting material thus.Liquid raw material supply to being set in 300 ℃ the vaporizer, is made liquid starting material evaporation thus.Utilize hydrogen be used as carrier gas with the gasification raw material supply to make by SiC, be heated to 1,200 ℃ Reaktionsofen (internal diameter: 120mm φ, highly: 2,000mm) in.Raw-material supply rate is 10g/min, and the flow velocity of hydrogen is 60L/min.
Will by the product (80g) that above method obtains pack into the crucible that graphite makes (internal diameter: 100mm φ, highly: 150mm), and 1000 ℃ of bakings 1 hour down in argon gas atmosphere.Then, in argon gas atmosphere, make products obtained therefrom carry out greying 30 minutes under 2,800 ℃.
The production of carbon fiber 3:
With Henschel mixing machine mixing 98g carbon fiber and 2g B4C, this carbon fiber by with the production of carbon fiber 1 in identical reaction and fire to handle and obtain.With the 100g mixture pack into the crucible that graphite makes (internal diameter: 100mm φ, highly: 150mm), and in argon gas atmosphere, make it carry out greying 30 minutes under 2,800 ℃.
The production of carbon fiber 4:
Benzene, ferrocene and thiophene (mass ratio: 92: 7: 1) is admixed together, prepare liquid starting material thus.Liquid raw material supply to being set in 300 ℃ the vaporizer, is made liquid starting material evaporation thus.Utilize hydrogen be used as carrier gas with the gasification raw gas be fed to make by SiC, be heated to 1,200 ℃ Reaktionsofen (internal diameter: 120mm φ, highly: 2,000mm) in.Raw-material supply rate is 8g/min, and the flow velocity of hydrogen is 80L/min.
Will by the product (80g) that above method obtains pack into the crucible that graphite makes (internal diameter: 100mm φ, highly: 150mm), and 1000 ℃ of bakings 1 hour down in argon gas atmosphere.Then, in argon gas atmosphere, make products obtained therefrom carry out greying 30 minutes under 2,800 ℃.
The production of carbon fiber 5:
Benzene, ferrocene and sulphur (mass ratio: 96: 3: 1) is admixed together, prepare liquid starting material thus.Utilize hydrogen be used as carrier gas with 80 ° jet angle with liquid starting material be ejected into make by SiC, be heated to 1,250 ℃ Reaktionsofen (internal diameter: 120mm φ, highly: 2,000mm) in.Raw-material supply rate is 70g/min, and the flow velocity of hydrogen is 60L/min.
Will by the product (80g) that above method obtains pack into the crucible that graphite makes (internal diameter: 100mm φ, highly: 150mm), and 1000 ℃ of bakings 1 hour down in argon gas atmosphere.Then, in argon gas atmosphere, make products obtained therefrom carry out greying 30 minutes under 2,800 ℃.
The production of carbon fiber:
With the mixture of ethylene gas and hydrogen and diameter for the aluminum oxide of about 2nm support iron be fed to that quartz is made, be heated to 800 ℃ reaction tubes (internal diameter: 60mm φ, highly: 1,000mm) in.The flow velocity of ethene and hydrogen is respectively 2L/min and 1L/min.
Embodiment 1
Use Labo-Plastmill (by Toyo Seiki Co., Ltd. make) under 240 ℃ and 80rpm, 10 minutes (mixing energies: 850MJ/m of carbon fiber of the polycarbonate resin of melt kneading 90 quality % (by Mitsubishi Gas ChemicalCompany, the Iupilon H4000 that Inc. makes) and 10 quality % 3), use 50t thermal forming device (making) at 250 ℃ temperature, 200kgf/cm then by Nippo Engineering Co.Ltd. 2Pressure and the condition of time of 30 seconds under, it is molded as the plate of 10mm * 10mm * 2mm, obtain composition 1 thus.The optical microscopy map of the cross section of plate as shown in Figure 1, the analytical results of agglomerate diameter is as shown in Figure 2 in the microgram.
Embodiment 2
Mediate polycarbonate resin (by Mitsubishi GasChemical Company, the Iupilon H4000 that Inc. makes) and carbon fiber 2 (mixing energy: 950MJ/m in the mode identical with embodiment 1 3), molded then, obtain composition 2 thus.
Embodiment 3
Mediate polycarbonate resin (by Mitsubishi GasChemical Company, the Iupilon H4000 that Inc. makes) and carbon fiber 3 (mixing energy: 820MJ/m in the mode identical with embodiment 1 3), molded then, obtain composition 3 thus.
Embodiment 4
Mediate polycarbonate resin (by Mitsubishi GasChemical Company, the Iupilon H4000 that Inc. makes) and carbon fiber 4 (mixing energy: 980MJ/m in the mode identical with embodiment 1 3), molded then, obtain composition 4 thus.
Comparative Examples 1
Mediate polycarbonate resin (by Mitsubishi GasChemical Company, the Iupilon H4000 that Inc. makes) and carbon fiber 5 (mixing energy: 800MJ/m in the mode identical with embodiment 1 3), molded then, obtain composition 5 thus.
Comparative Examples 2
Mediate polycarbonate resin (by Mitsubishi GasChemical Company, the Iupilon H4000 that Inc. makes) and carbon fiber 6 (mixing energy: 1120MJ/m in the mode identical with embodiment 1 3), molded then, obtain composition 6 thus.
The physical properties of carbon fiber 1～6 is as shown in table 1.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative Examples 1 Comparative Examples 2
Carbon fiber 1 Carbon fiber 2 Carbon fiber 3 Carbon fiber 4 Carbon fiber 5 Carbon fiber 6
Fibre diameter (nm) 200 90 200 60 300 20
Staple length (μ m) 12 20 12 12 9 3
Length-to-diameter ratio (-) 60 222 60 200 30 150
Branch degree (branch amount/one filament) 1 4 1 1 25 0
Specific surface area (m 2/g) 10 22 10 38 7 100
d 002(nm) 0.340 0.342 0.338 0.343 0.340 0.348
Id/Ig(-) 0.2 0.1 1.0 0.1 0.3 0.5
The physical properties of the composition 1～6 that obtains in embodiment 1～4 and Comparative Examples 1 and 2 is as shown in table 2.
Table 2
Embodiment No. 1 2 3 4 Comparative Examples 1 Comparative Examples 2
Composition No. 1 2 3 4 5 6
Mixing energy (MJ/m 3) 850 950 820 980 800 1120
Average agglomerate diameter (μ m) 3.2 6.3 2.4 4.3 10.9 3.8
The volume ratio of an agglomerate and a carbon fiber 35 330 20 1230 50000 16000
Area is than (%) 0.9 1.5 1.0 2.3 8.5 7.3
Volume resistance (Ω cm) 1.2×10 8 3.5×10 2 6.8×10 5 2.2×10 1 3.5×10 15 4.4×10 2
Composition/material resin (ratio of cantilever shock resistance) 1.05 0.95 1.00 0.90 0.65 0.40
Industrial applicibility
In conductive resin composition of the present invention, carbon fiber disperses equably and does not form agglomerate, therefore adds a small amount of carbon fiber, can obtain good electric conductivity and engineering properties is descended.
In addition, conductive resin composition of the present invention can be widely used as various secondary cells, such as dry cell, Pb battery, capacitor or up-to-date lithium rechargeable battery; Transparency electrode; Electromagnetic shielding; Anti-static material; Electrically-conducting paint; Electroconductive binder etc.

Claims (17)

1, a kind of conductive resin composition, it comprises the carbon fiber of 1～30 quality % and the resin of 99～70 quality %, this carbon fiber has hollow structure, average filament diameter is 50～500nm, average aspect ratio is 50～1000, and wherein the volume ratio (volume of the volume of carbon fiber agglomerate/carbon fiber filament) of a carbon fiber filament of carbon fiber agglomerate and formation agglomerate is 1500 or littler in the resin combination.
2, according to the conductive resin composition of claim 1, wherein the BET specific surface area of carbon fiber is 3～50m 2/ g, mean level of the sea spacing d 0002Be 0.345nm or littler, and in raman scattering spectrum, 1341～1349cm -1Bands of a spectrum (Id) and 1570～1578cm -1The ratio of peak (Id/Ig) of bands of a spectrum (Id) be 0.1～1.4.
3, according to the conductive resin composition of claim 1, wherein every of carbon fiber filament have 5 or still less from the branched part of filament surfaces.
4, according to the conductive resin composition of claim 1, wherein resin is thermoplastic resin, thermosetting resin or light-cured resin.
5, according to the conductive resin composition of claim 1, wherein the mean diameter of carbon fiber agglomerate is 0.2～10 μ m in the resin combination.
6, according to the conductive resin composition of claim 1, wherein the area ratio of carbon fiber agglomerate in any cross section of resin combination is 5% or littler.
7, according to the conductive resin composition of claim 1, wherein the volume resistance value is 10 10Ω cm or littler.
8, according to the conductive resin composition of claim 7, wherein resin combination is 0.9 or bigger with the ratio (conductive resin composition/resinogen material) of the raw-material shock resistance value of resin.
9, a kind of method of producing conductive resin composition, wherein the carbon fiber with 1～30 quality % mixes with the molten thermoplastic resin of 99～70 quality %, and this carbon fiber has hollow structure, and average filament diameter is 50～500nm, average aspect ratio is 50～1000, and mixing energy is 1000MJ/m 3Or it is littler.
10, a kind of method of producing conductive resin composition, wherein with the liquid thermosetting mixed with resin of carbon fiber and 99～70 quality % of 1～30 quality %, this carbon fiber has hollow structure, and average filament diameter is 50～500nm, average aspect ratio is 50～1000, and mixing energy is 1000MJ/m 3Or it is littler.
11, a kind of method of producing conductive resin composition, wherein the carbon fiber with 1～30 quality % mixes with the liquid light-cured resin precursor of 99～70 quality %, this carbon fiber has hollow structure, average filament diameter is 50～500nm, average aspect ratio is 50～1000, and mixing energy is 1000MJ/m 3Or it is littler.
12, a kind of method of producing conductive resin composition, wherein supply the thermoplastic resin particle of 99～70 quality % from the hopper of kneader, and the carbon fiber of side loading 1～30 quality %, this carbon fiber has hollow structure, average filament diameter is 50～500nm, and average aspect ratio is 50～1000.
13, a kind of method of producing conductive resin composition, the thermoplastic resin powder who wherein supplies 99～70 quality % mixes with the carbon fiber of 1～30 quality %, this carbon fiber has hollow structure, average filament diameter is 50～500nm, average aspect ratio is 50～1000, then mixture is carried out melt kneading.
14, a kind of method of producing conductive resin composition, wherein the thermosetting resin with 99～70 quality % mixes with the carbon fiber of 1～30 quality %, and this carbon fiber has hollow structure, and average filament diameter is 50～500nm, average aspect ratio is 50～1000, then mixture is carried out thermofixation.
15, use the antistatic material of each described conductive resin composition in the claim 1～8.
16, use the electrically conducting coating of each described conductive resin composition in the claim 1～8.
17, use the electroconductive binder of each described conductive resin composition in the claim 1～8.
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